Fluorinated compound, fluoropolymer and method for producing the compound

ABSTRACT

To provide a novel fluorinated compound, a fluoropolymer and a method for producing the compound. 
     A compound represented by the formula CF 2 ═CFCF 2 C(X)(C(O)OZ)(CH 2 ) n CR═CHR (wherein X is a hydrogen atom, a cyano group or a group represented by the formula —C(O)OZ, Z is a hydrogen atom or a C 1-20  monovalent organic group, n is 0, 1, or 2, and R is a hydrogen atom or a C 1-20  monovalent organic group), a method for producing it, and a fluoropolymer obtained by polymerizing the compound.

TECHNICAL FIELD

The present invention relates to a novel fluorinated compound, afluoropolymer and a method for producing the compound.

BACKGROUND ART

A fluoropolymer containing repeating units having a fluorinatedalicyclic structure in its main chain is excellent in physicalproperties such as optical characteristics (such as transparency anddurable light resistance) and water and oil repellency.

As a cyclic polymerizable compound which forms the above repeatingunits, a polyfluoroalkenyl vinyl ether such as CF₂═CFOCF₂CF₂CF═CF₂ hasbeen known (e.g. Patent Document 1).

Further, a fluoropolymer containing repeating units having a fluorinatedalicyclic structure in its main chain and having a functional group isexcellent in the above physical properties and in addition, physicalproperties derived from the above functional group can be developed, andsuch a polymer is applied to various fields (e.g. a resist material forlithography) (e.g. Patent Document 2).

As a cyclic polymerizable compound which forms the above repeatingunits, Patent Document 2 discloses a fluoroalkadiene having a functionalgroup (such as CF₂═CFCF₂C(CF₃)(OH)CH₂CH═CH₂).

Further, as a fluoroalkadiene having a group analogues to a carboxylgroup, Patent Document 3 discloses1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene(CF₂═CFCH₂CH(C(O)OC(CH₃)₃)CH₂CH═CH₂ or the like).

Patent Document 1: JP-A-01-131215

Patent Document 2: WO02/064648

Patent Document 3: JP-A-2005-298707

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention

As a fluoroalkadiene having a functional group, compounds having variousstructures have been desired depending on the purpose of use of theresulting polymer. However, even if such a compound is to be obtained inpractice, it is difficult to obtain material compounds in many cases,and such a compound is not necessarily easily obtained.

Further, also with respect to a fluoroalkadiene having a group analoguesto a carboxyl group, only the above compound as disclosed in PatentDocument 3 has been known, and no other compounds have been known.

Means to Solve the Problems

The present invention has been made to solve the above problems andprovides a novel fluoroalkadiene having a carboxyl group or a groupanalogues thereto, such as1,1,2,3,3-pentafluoro-4-alkoxycarbonyl-1,6-heptadiene, a polymer thereofand a method for producing the compound.

That is, the present invention provides the following.

1. A compound represented by the following formula (1):CF₂═CFCF₂C(X)(C(O)OZ)(CH₂)_(n)CR═CHR  (1)wherein X is a hydrogen atom, a cyano group or a group represented bythe formula —C(O)OZ; Z is a hydrogen atom or a C₁₋₂₀ monovalent organicgroup; n is 0, 1 or 2; and R is a hydrogen atom or a C₁₋₂₀ monovalentorganic group, provided that two R's may be the same or different.2. A compound represented by the following formula (11):CF₂═CFCF₂CH(C(O)OZ¹)CH₂CH═CH₂  (11)wherein Z¹ is a hydrogen atom, a group represented by the formula—C(Y¹)₃, a group represented by the formula —CH₂OY² or a grouprepresented by the following formula:

each of Y¹ and Y² which are independent of each other, is a hydrogenatom or a C₁₋₁₉ monovalent saturated hydrocarbon group; Y³ is a hydrogenatom or a C₁₋₁₆ monovalent saturated hydrocarbon group; and Q³ is aC₃₋₁₉ group which forms a bivalent cyclic hydrocarbon group incombination with the carbon atom in the formula, provided that in Y¹, Y²and Y³ in the case of a monovalent saturated hydrocarbon group and Q³,between the carbon atom-carbon atom, a group represented by the formula—O—, a group represented by the formula —C(O)— or a group represented bythe formula —C(O)O— may be inserted, and to a carbon atom in Y¹, Y², Y³and Q³, a fluorine atom, a hydroxyl group or a carboxyl group may bebonded.3. A compound represented by the following formula (111):CF₂═CFCF₂CH(C(O)OZ¹¹)CH₂CH═CH₂  (111)wherein Z¹¹ is a hydrogen atom, a group represented by the formula—C(Y¹¹)₃, a group represented by the formula —CH₂OY²¹ or a grouprepresented by the formula:

Y¹¹ is a C₁₋₆ monovalent saturated hydrocarbon group, Y²¹ is a C₁₋₁₂monovalent saturated hydrocarbon group or a C₂₋₁₂ monovalent saturatedhydrocarbon group containing a group represented by the formula —O—; Y³¹is a hydrogen atom or a C₁₋₆ monovalent saturated hydrocarbon group; andQ³¹ is a C₄₋₁₂ a bivalent saturated hydrocarbon group, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent saturatedhydrocarbon group having a group represented by the formula —O—, a grouprepresented by the formula —C(O)— or a group represented by the formula—C(O)O— inserted between the carbon atom-carbon atom.4. A compound represented by the following formula (1111):CF₂═CFCF₂CH(C(O)OZ¹¹¹)CH₂CH═CH₂  (1111)wherein Z¹¹¹ is a C₃₋₂₀ monovalent organic group having at least onegroup represented by the formula —C(CF₃)₂OH.5. A compound represented by the following formula (12):CF₂═CFCF₂C(C(O)OZ¹)₂CH₂CH═CH₂  (12)wherein Z¹ is a hydrogen atom, a group represented by the formula—C(Y¹)₃, a group represented by the formula —CH₂OY² or a grouprepresented by the following formula:

each of Y¹ and Y² which are independent of each other, is a hydrogenatom or a C₁₋₁₉ monovalent saturated hydrocarbon group; Y³ is a hydrogenatom or a C₁₋₁₆ monovalent saturated hydrocarbon group; and Q³ is aC₃₋₁₉ group which forms a bivalent cyclic hydrocarbon group incombination with the carbon atom in the formula, provided that in Y¹, Y²and Y³ in the case of a monovalent saturated hydrocarbon group and Q³,between the carbon atom-carbon atom, a group represented by the formula—O—, a group represented by the formula —C(O)— or a group represented bythe formula —C(O)O— may be inserted, and to a carbon atom in Y¹, Y², Y³and Q³, a fluorine atom, a hydroxyl group or a carboxyl group may bebonded.6. A compound represented by the following formula (121):CF₂═CFCF₂C(C(O)OZ¹¹)₂CH₂CH═CH₂  (121)wherein Z¹¹ is a hydrogen atom, a group represented by the formula—C(Y¹¹)₃, a group represented by the formula —CH₂OY²¹ or a grouprepresented by the following formula:

Y¹¹ is a C₁₋₆ monovalent saturated hydrocarbon group; Y²¹ is a C₁₋₁₂monovalent saturated hydrocarbon group or a C₂₋₁₂ monovalent saturatedhydrocarbon group containing a group represented by the formula —O—; Y³¹is a hydrogen atom or a C₁₋₆ saturated hydrocarbon group; and Q³¹ is aC₄₋₁₂ a bivalent saturated hydrocarbon group, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent saturatedhydrocarbon group having a group represented by the formula —O—, a grouprepresented by the formula —C(O)— or a group represented by the formula—C(O)O— inserted between the carbon atom-carbon atom.7. A method for producing a compound represented by the followingformula (p12), which comprises reacting a compound represented by thefollowing formula (p5) with a compound represented by the followingformula (p4) to obtain a compound represented by the following formula(p3), and then reacting the compound with a compound represented by thefollowing formula (p2):CH₂(C(O)OZ^(P))₂  (p5)CHR═CR(CH₂)_(n)-G^(P)  (p4)CH(C(O)OZ^(P))₂((CH₂)_(n)CR═CHR)  (p3)CF₂═CFCF₂-J^(P)  (p2)CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12)wherein Z^(P) is a C₁₋₂₀ monovalent organic group; R is a hydrogen atomor a C₁₋₂₀ monovalent organic group, provided that two R's may be thesame or different; n is 0, 1 or 2; G^(P) is a chlorine atom, a bromineatom or an iodine atom; J^(P) is a chlorine atom, a bromine atom, aniodine atom or a group represented by the formula —OSO₂-L^(P); and L^(P)is a fluorine atom, a C₁₋₁₀ hydrocarbon group or a C₁₋₁₀ fluorinatedhydrocarbon group.8. A method for producing a compound represented by the followingformula (12H), which comprises hydrolyzing a compound represented by thefollowing formula (p12):CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12)CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)wherein Z^(P) is a C₁₋₂₀ monovalent organic group; R is a hydrogen atomor a C₁₋₂₀ monovalent organic group, provided that two R's may be thesame or different; and n is 0, 1 or 2.9. A method for producing a compound represented by the followingformula (11H), which comprises decarboxylation of a compound representedby the following formula (12H):CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)CF₂═CFCF₂CH(C(O)OH)(CH₂)_(n)CR═CHR  (11H)wherein R is a hydrogen atom or a C₁₋₂₀ monovalent organic group,provided that two R's may be the same or different; and n is 0, 1 or 2.10. A method for producing a compound represented by the followingformula (12W), which comprises reacting a compound represented by thefollowing formula (12H) with a compound represented by the followingformula (w):CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)CH₂═CW^(P) ₂  (w)CF₂═CFCF₂C(C(O)OC(CH₃)W^(P) ₂)₂(CH₂)_(n)CR═CHR  (12W)wherein R is a hydrogen atom or a C₁₋₂₀ monovalent organic group,provided that two R's may be the same or different; n is 0, 1 or 2; andW^(P) is each independently a hydrogen atom or a C₁₋₂₀ monovalentsaturated hydrocarbon group, or two W^(P)'s are groups which form aC₃₋₂₀ bivalent cyclic hydrocarbon group in combination with the carbonatom in the formula.11. A method for producing a compound represented by the followingformula (11W), which comprises reacting a compound represented by thefollowing formula (11H) with a compound represented by the followingformula (w):CF₂═CFCF₂CH(C(O)OH)(CH₂)_(n)CR═CHR  (11H)CH₂═CW^(P) ₂  (w)CF₂═CFCF₂CH(C(O)OC(CH₃)W^(P) ₂)(CH₂)_(n)CR═CHR  (11W)wherein R is a hydrogen atom or a C₁₋₂₀ monovalent organic group,provided that two R's may be the same or different; n is 0, 1 or 2; andW^(P) is each independently a hydrogen atom or a C₁₋₂₀ monovalentsaturated hydrocarbon group, or two W^(P)'s are groups which form aC₃₋₂₀ bivalent cyclic hydrocarbon group in combination with the carbonatom in the formula.12. A polymer obtained by polymerizing a compound represented by theformula (1).13. A polymer obtained by polymerizing a compound represented by thefollowing formula (2):CF₂═CFCF₂CH(C(O)OZ¹¹¹)(CH₂)_(n)CR═CHR  (2)wherein Z¹¹¹ is a C₃₋₂₀ monovalent organic group having at least onegroup represented by the formula —C(CF₃)₂OH; n is 0, 1 or 2; and R is ahydrogen atom or a C₁₋₂₀ monovalent organic group, provided that two R'smay be the same or different.14. The polymer according to the above 12 or 13, which has a weightaverage molecular weight of from 1,000 to 1,000,000.

EFFECTS OF THE INVENTION

According to the present invention, a cyclic polymerizable compound toform repeating units having a fluorinated alicyclic structure in itsmain chain and having a carboxyl group or a group analogues thereto, isprovided. The polymer of the present invention has a high fluorinecontent and is thereby particularly excellent in water and oilrepellency and optical characteristics (such as transparency and durablelight resistance).

BEST MODE FOR CARRYING OUT THE INVENTION

In the present specification, a compound represented by the formula (1)will sometimes be referred to as a compound (1), and a group representedby the formula —C(Y¹)₃ will be referred to as —C(Y¹)₃. The same appliesto other compounds and other groups. Further, symbols in groups are asdefined above unless otherwise specified.

The present invention provides the following compound (1):CF₂═CFCF₂C(X)(C(O)OZ)(CH₂)_(n)CR═CHR  (1)

In the compound (1), X is a hydrogen atom, a cyano group or a formula—C(O)OZ. Among them, X is preferably a hydrogen atom or —C(O)OZ.

In the compound (1), Z is a hydrogen atom or a C₁₋₂₀ monovalent organicgroup. Among them, Z is preferably Z¹. This Z¹ is a hydrogen atom,—C(Y¹)₃ (hereinafter sometimes referred to as a group (Y1)), —CH₂OY²(hereinafter sometimes referred to as a group (Y2)) or a grouprepresented by the following formula (hereinafter sometimes referred toas a group (Y3) and sometimes abbreviated as —C(Y³)(=Q³)):

Further, Z is more preferably Z¹¹. This Z¹¹ is a hydrogen atom,—C(Y¹¹)₃, —CH₂OY²¹ or —C(Y³¹)(=Q³¹). Further, Z is also preferably agroup (Z¹¹¹) having at least one group represented by the formula—C(CF₃)₂OH (bistrifluoromethylcarbinol group).

Each of Y¹, Y² and Y³ which are independent of one another, in a casewhere they are not a hydrogen atom, may be a non-cyclic group or may bea group containing a cyclic group. The non-cyclic group may be a lineargroup or may be a branched group. The group containing a cyclic groupmay be a group containing a polycyclic group or may be a groupcontaining a monocyclic group. The group containing a polycyclic groupmay be a group containing a bridged cyclic group or may be a groupcontaining a condensed cyclic group.

As specific examples of the group containing a cyclic group, a groupcontaining each of the following groups or a group having a hydrogenatom in such a group substituted by a fluorine atom may be mentioned.

As specific examples of the group having a hydrogen atom in the groupcontaining a cyclic group substituted by a fluorine atom, the followinggroups may be mentioned.

In the group (Y1), the three Y¹'s may be the same or different.

Each of the three Y¹'s is a hydrogen atom or a C₁₋₁₉ monovalentsaturated hydrocarbon group. Further, in Y¹ in the case of a monovalentsaturated hydrocarbon group, between the carbon atom-carbon atom, agroup represented by the formula —O— (etheric oxygen atom), a grouprepresented by the formula —C(O)— (carbonyl group) or a grouprepresented by the formula —C(O)O— (ester group) may be inserted.Further, to a carbon atom in Y¹, a fluorine atom, a hydroxyl group or acarboxyl group may be bonded. Further, Y¹ preferably has at least onebistrifluoromethylcarbinol group.

The three Y¹'s are preferably such a combination that two are C₁₋₆monovalent saturated hydrocarbon groups and one is a C₁₋₁₂ monovalentcyclic saturated hydrocarbon group, such a combination that two arehydrogen atoms and one is a C₁₋₁₂ polyfluoroalkyl group, or such acombination that three are C₁₋₆ monovalent saturated hydrocarbon groups(Y¹¹). Further, three Y¹'s are particularly preferably such acombination that two are C₁₋₆ alkyl groups (preferably a methyl group)and one is a 1-adamantyl group, such a combination that they arepolyfluoroalkyl groups represented by the formula —CH₂R^(FY) (whereinR^(FY) is a C₁₋₁₀ perfluoroalkyl group), or such a combination thatthree are C₁₋₆ alkyl groups (preferably a methyl group).

Y² in the group (Y2) is a hydrogen atom or a C₁₋₁₉ monovalent saturatedhydrocarbon group, provided that in Y² in the case of a monovalentsaturated hydrocarbon group, between the carbon atom-carbon atom, agroup represented by the formula —O—, a group represented by the formula—C(O)— or a group represented by the formula —C(O)O— may be inserted.Further, to a carbon atom in Y², a fluorine atom, a hydroxyl group or acarboxyl group may be bonded. Further, Y² preferably has at least onebistrifluoromethylcarbinol group.

Y² is preferably a C₁₋₁₂ monovalent saturated hydrocarbon group, a C₂₋₁₂monovalent saturated hydrocarbon group containing —O—, a C₁₋₁₂monovalent fluorinated saturated hydrocarbon group or a C₂₋₁₂ monovalentfluorinated saturated hydrocarbon group containing —O—. Among them, Y²is more preferably Y²¹ (a C₁₋₁₂ monovalent saturated hydrocarbon groupor a C₂₋₁₂ monovalent saturated hydrocarbon group containing —O—).

As specific examples of the group (Y2), the following groups may bementioned.

Y³ in the group (Y3) is a hydrogen atom or a C₁₋₁₆ monovalent saturatedhydrocarbon group, provided that in Y³ in the case of a monovalentsaturated hydrocarbon group, between the carbon atom-carbon atom, agroup represented by the formula —O—, a group represented by the formula—C(O)— or a group represented by the formula —C(O)O— may be inserted.Further, to a carbon atom in Y³, a fluorine atom, a hydroxyl group or acarboxyl group may be bonded. Further, Y³ preferably has at least onebistrifluoromethylcarbinol group.

Y³ is preferably a hydrogen atom, a C₁₋₆ monovalent saturatedhydrocarbon group or a C₂₋₆ monovalent saturated hydrocarbon groupcontaining —O—. Among them, Y³ is more preferably Y³¹ (a hydrogen atomor a C₁₋₆ monovalent saturated hydrocarbon group).

Q³ in the group (Y3) is a C₃₋₁₉ group which forms a bivalent cyclichydrocarbon group in combination with the carbon atom in the formula,provided that between the carbon atom-carbon atom in Q³, a grouprepresented by the formula —O—, a group represented by the formula—C(O)— or a group represented by the formula —C(O)O— may be inserted.Further, to a carbon atom in Q³, a fluorine atom, a hydroxyl group or acarboxyl group may be bonded. Further, Q³ preferably has at least onebistrifluoromethylcarbinol group.

Q³ may be a group which forms a bivalent monocyclic hydrocarbon group incombination with the carbon atom in the formula or may be a group whichforms a bivalent polycyclic hydrocarbon group in combination with thecarbon atom in the formula. The polycyclic hydrocarbon group may be acondensed cyclic hydrocarbon group or may be a bridged cyclichydrocarbon group. Q³ is preferably a saturated group.

Q³ is preferably a C₄₋₁₂ bivalent saturated hydrocarbon group, a C₄₋₁₂bivalent saturated hydrocarbon group having —O—, —C(O)— or —C(O)O—inserted between the carbon atom-carbon atom, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent fluorinatedsaturated hydrocarbon group having —O—, —C(O)— or —C(O)O— insertedbetween the carbon atom-carbon atom. Among them, Q³ is more preferablyQ³¹ (a C₄₋₁₂ bivalent saturated hydrocarbon group, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent saturatedhydrocarbon group having —O—, —C(O)— or —C(O)O— inserted between thecarbon atom-carbon atom).

As specific example of the group (Y3), groups represented by thefollowing formulae may be mentioned.

In the compound (1), n is 0, 1 or 2, preferably 1.

In the compound (1), R is a hydrogen atom or a C₁₋₂₀ monovalent organicgroup, provided that two R's may be the same or different. It ispreferred that both the two R's are hydrogen atoms.

R which is a C₁₋₂₀, preferably C₁₋₁₂ monovalent organic group, ispreferably a C₁₋₁₂ monovalent saturated hydrocarbon group. Themonovalent saturated hydrocarbon group may be a non-cyclic group or maybe a cyclic group. The non-cyclic group may be a linear group or may bea branched group. The cyclic group may be a polycyclic group or may be amono group. The polycyclic group may be a bridged cyclic group or may bea condensed cyclic group.

In the monovalent saturated hydrocarbon group as R, between the carbonatom-carbon atom, —O— may be inserted. Further, to a carbon atom in themonovalent saturated hydrocarbon group, a fluorine atom, a hydroxylgroup or a carboxyl group may be bonded.

The compound (1) is preferably the following compound (11) or thefollowing compound (12):CF₂═CFCF₂CH(C(O)OZ¹)CH₂CH═CH₂  (11)CF₂═CFCF₂C(C(O)OZ¹)₂CH₂CH═CH₂  (12)

Further, the compound (11) is preferably the following compound (111),and the compound (12) is preferably the following compound (121):CF₂═CFCF₂CH(C(O)OZ¹¹)CH₂CH═CH₂  (111)CF₂═CFCF₂C(C(O)OZ¹¹)₂CH₂CH═CH₂  (121)

Further, the compound (1) is preferably the following compound (2),particularly preferably the compound (1111):CF₂═CFCF₂CH(C(O)OZ¹¹¹)(CH₂)_(n)CR═CHR  (2)CF₂═CFCF₂CH(C(O)OZ¹¹¹)CH₂CH═CH₂  (1111)

As specific examples of the compound (1), the following compounds may bementioned. Specific examples of the compound (1) wherein Z is a hydrogenatom:CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂CF₂═CFCF₂C(C(O)OH)₂CH₂CH═CH₂CF₂═CFCF₂C(CN)(C(O)OH)CH₂CH═CH₂

Specific examples of the compound (1) wherein Z is the group (Y1):CF₂═CFCF₂CH(C(O)OC(CH₃)₃)CH₂CH═CH₂CF₂═CFCF₂C(C(O)OC(CH₃)₃)₂CH₂CH═CH₂CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)OH)CH₂CH═CH₂CF₂═CFCF₂CH(C(O)OCH(CH₃)C(CF₃)₂OH)CH₂CH═CH₂CF₂═CFCF₂CH(C(O)OCH(CH₂C(CF₃)₂OH)₂)CH₂CH═CH₂CF₂—CFCF₂C(CN)(C(O)OC(CH₃)₃)CH₂CH═CH₂CF₂═CFCF₂CH(C(O)OCH₂CF₂CF₃)CH₂CH═CH₂Specific examples of the compound (1) wherein Z is the group (Y2):

Specific examples of the compound (1) wherein Z is the group (Y3):

The present invention provides a method for producing the followingcompound (p12), which comprises reacting the following compound (p5)with the following compound (p4) to obtain the following compound (p3),and then reacting the compound (p3) with the following compound (p2):CH₂(C(O)OZ^(P))₂  (p5)CHR═CR(CH₂)_(n)-G^(P)  (p4)CH(C(O)OZ^(P))₂((CH₂)_(n)CR═CHR)  (p3)CF₂═CFCF₂-J^(P)  (p2)CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12)

Z^(P) is a C₁₋₂₀ monovalent organic group. Z^(P) is preferably a C₁₋₂₀monovalent saturated hydrocarbon group which may contain —O—, —C(O)— or—C(O)O—. Further, Z^(P) is particularly preferably a C₁₋₆ alkyl group.

R and n are as defined above.

G^(P) is a chlorine atom, a bromine atom or an iodine atom, preferably achorine atom or a bromine atom.

J^(P) is a chlorine atom, a bromine atom, an iodine atom or a grouprepresented by the formula —OSO₂-L^(P). Further, L^(P) is a fluorineatom, a C₁₋₁₀ hydrocarbon group or a C₁₋₁₀ fluorinated hydrocarbongroup. L^(P) in J^(P) is preferably a fluorine atom, a methyl group, atrifluoromethyl group or a 4-methyl-phenyl group, particularlypreferably a fluorine atom.

The reaction of the compound (p5) with the compound (p4) is carried outpreferably in the presence of a basic compound. The basic compound isnot particularly limited and is preferably a metal hydride, particularlypreferably NaH, NaBH₄ or LiAlH₄.

The above reaction is carried out preferably in the presence of anaprotic solvent. The aprotic solvent may, for example, be specificallydiethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane,monoglyme, diglyme, triglyme, tetraglyme, acetonitrile, benzonitrile,sulfolane, dimethylformamide, dimethylacetamide or dimethylsulfoxide.

The reaction temperature is not particularly limited and is preferablyfrom −78° C. to +25° C. The reaction pressure is not particularlylimited.

The reaction of the compound (p3) with the compound (p2) is carried outpreferably in the presence of a basic compound. Further, the reaction iscarried out preferably in the presence of an aprotic solvent. Thereaction temperature is not particularly limited and is preferably from−78° C. to +25° C. The reaction pressure is not particularly limited.Further, specific examples of the basic compound and specific examplesof the aprotic solvent are the same as those in the reaction of thecompound (p5) with the compound (p4).

As specific examples of the compound (p5), CH₂(C(O)OCH₃)₂,CH₂(C(O)OCH₂CH₃)₂, CH₂(C(O)OC(Y¹)₃)₂, CH₂(C(O)OCH₂OY²)₂ and thefollowing compound may be mentioned. Y¹ and Y² are as defined above.

As specific examples of the compound (p4), CH₂═CHCH₂Cl, CH₂═CHCH₂Br,CH₂═CHCH₂CH₂Cl and CH₂═CHCH₂CH₂Br may be mentioned.

As specific examples of the compound (p3), CH(C(O)OCH₃)₂(CH₂CH═CH₂),CH(C(O)OCH₂CH₃)₂(CH₂CH═CH₂), CH(C(O)OC(Y¹)₃)₂(CH₂CH═CH₂),CH(C(O)OCH₂OY²)₂(CH₂CH═CH₂) and the following compound may be mentioned.

As specific examples of the compound (p2), CF₂═CFCF₂OSO₂F may bementioned.

As specific examples of the compound (p12),CF₂═CFCF₂C(C(O)OCH₃)₂CH₂CH═CH₂, CF₂═CFCF₂C(C(O)OCH₂CH₃)₂CH₂CH═CH₂,CF₂═CFCF₂C(C(O)OC(Y¹)₃)₂CH₂CH═CH₂, CF₂═CFCF₂C(C(O)OCH₂OY²)₂CH₂CH═CH₂ andthe following compound may be mentioned:

Further, the compound (p12) may be prepared by reacting the compound(p5) with the compound (p2) to obtain the following compound (p3F), andthen reacting the compound (p3F) with the compound (p4):CH(C(O)OZ^(P))₂(CF₂CF═CF₂)  (p3F)

The present invention provides a method for producing the followingcompound (12H), which comprises hydrolyzing the compound (p12):CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)

The hydrolysis of the compound (p12) is carried out preferably underacidic conditions, particularly preferably in the presence of a proticacid. The protic acid may be an inorganic acid or may be an organicacid. As specific examples of the protic acid, a carboxylic acid and asulfonic acid may be mentioned.

Further, the hydrolysis may be carried out in the presence of a solventor may be carried out in the absence of a solvent. The temperature atthe hydrolysis is not particularly limited and is preferably from −78°C. to +25° C. The reaction pressure is not particularly limited.

The present invention provides a method for producing the followingcompound (11H) which comprises decarboxylation of the compound (12H):CF₂═CFCF₂CH(C(O)OH)(CH₂)_(n)CR═CHR  (11H)

The decarboxylation of the compound (12H) is carried out preferably byheating the compound (12H). The temperature at the time of heating thecompound (12H) is preferably from 50 to 200° C. Further, the pressure atthe time of heating the compound (12H) is not particularly limited.

The present invention provides a method for producing the followingcompound (12W), which comprises reacting the compound (12H) with thefollowing compound (w), and a method for producing the followingcompound (11W), which comprises reacting the compound (11H) with thefollowing compound (w):CR¹R²═CW^(P) ₂  (w)CF₂═CFCF₂C(C(O)OC(CH₃)W^(P) ₂)₂(CH₂)_(n)CR═CHR  (12W)CF₂═CFCF₂CH(C(O)OC(CH₃)W^(P) ₂)(CH₂)_(n)CR═CHR  (11W)

In the above, each of R¹ and R² which may be the same or different, is ahydrogen atom or a C₁₋₂₀, preferably C₁₋₁₂ monovalent organic group.Each of R¹ and R² is preferably a C₁₋₁₂ monovalent saturated hydrocarbongroup. The monovalent saturated hydrocarbon group may be a non-cyclicgroup or may be a cyclic group. The non-cyclic group may be a lineargroup or may be a branched group. The cyclic group may be a polycyclicgroup or may be a monocyclic group. The polycyclic group may be abridged cyclic group or may be a condensed cyclic group. Between thecarbon atom-carbon atom in the monovalent saturated hydrocarbon group,—O— may be inserted. Further, to a carbon atom in the monovalentsaturated hydrocarbon group, a fluorine atom, a hydroxyl group or acarboxyl group may be bonded. Further, it may have abistrifluoromethylcarbinol group.

The respective reactions are carried out preferably under acidicconditions. The temperature and the pressure in the respective reactionsare not particularly limited.

As specific examples of the compound (w), the following compounds may bementioned:

Further, the following compound (p12) or the following compound (p11)may be produced by reacting the compound (12H) or the compound (11H)with Z^(P)-OH or Z^(P)-Cl under acidic conditions:CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12)CF₂═CFCF₂CH(C(O)OZ^(P))(CH₂)_(n)CR═CHR  (p11)

Further, in a case where Z^(P)-OH is used, the carboxyl group in thecompound (12H) or (11H) is preferably activated by an activating agentsuch as dicyclohexylcarbodiimide.

As specific examples of the compound Z^(P)-OH, the following compoundsmay be mentioned.

The compound (1) of the present invention is a1,1,2,3,3-pentafluoro-4-carboxy-alkadiene not known in any literature,and is useful as a polymerizable compound.

The present invention provides a polymer obtained by polymerizing thecompound (1) (hereinafter sometimes referred to as a polymer of thepresent invention). The compound (1) is a cyclic polymerizable compound,and the polymer of the present invention is usually a fluoropolymercontaining at least one type of repeating units (U) selected from thegroup consisting of repeating units represented by the followingformulae (U1), (U2) and (U3):

The weight average molecular weight of the polymer of the presentinvention is not particularly limited and is preferably from 1,000 to1,000,000.

Polymerization of the compound (1) is carried out preferably in thepresence of a polymerization initiator.

The polymerization initiator is preferably a radical polymerizationinitiator, more preferably a peroxide, an azo compound or a persulfate,particularly preferably a peroxide.

As specific examples of the peroxide, C₆H₅C(O)OOC(O)C₆H₅,C₆F₅C(O)OOC(O)C₆F₅, CF₃CF₂CF₂C(O)OOC(O)CF₂CF₂CF₃,(CH₃)₃CC(O)OOC(O)C(CH₃)₃, (CH₃)₂CHC(O)OOC(O)CH(CH₃)₂,(CH₃)₃CC₆H₁₀C(O)OOC(O)C₆H₁₀C(CH₃)₃, (CH₃)₃COC(O)OOC(O)OC(CH₃)₃,(CH₃)₂CHOC(O)OOC(O)OCH(CH₃)₂ and (CH₃)₃CC₆H₁₀OC(O)OOC(O)OC₆H₁₀C(CH₃)₃may be mentioned (wherein C₆H₅ is a phenyl group, C₆F₅ is apentafluorophenyl group and C₆H₁₀ is a 1,4-cyclohexylene group).

The method for polymerizing the compound (1) is not particularlylimited, and is carried out preferably in accordance with apolymerization method such as a bulk polymerization method, a solutionpolymerization method, a suspension polymerization method or an emulsionpolymerization method.

In a case where a polymerization solvent is used for polymerization ofthe compound (1), the type of the polymerization solvent is notparticularly limited.

As specific examples of the polymerization solvent, aliphatichydrocarbons such as pentane, hexane and heptane; hydrocarbon alcoholssuch as methanol, ethanol, n-propanol, isopropanol and tert-butanol;hydrocarbon ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone and cyclohexanone; hydrocarbon ethers such as dimethylether, diethyl ether, methyl ethyl ether, methyl tert-butyl ether,diethylene glycol dimethyl ether and tetraethylene glycol dimethylether; alicyclic hydrocarbon ethers such as tetrahydrofuran and1,4-dioxane; nitriles such as acetonitrile; hydrocarbon esters such asmethyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, tert-butyl acetate, methyl propionate and ethyl propionate;aromatic hydrocarbons such as toluene and xylene; chlorinatedhydrocarbons such as methylene chloride, chloroform and carbontetrachloride; chlorofluorohydrocarbons such as R-113, R-113a, R-141b,R-225ca and R225-cb; fluorinated hydrocarbons such as1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane and1,1,1,2,2,3,3,4,4-nonafluorohexane; fluorinated hydrocarbon ethers suchas methyl 2,2,3,3-tetrafluoroethyl ether; and fluorinated hydrocarbonalcohols such as 2,2,2-trifluoroethanol,1,1,1,3,3,3-hexafluoroisopropanol, 2,2,3,3-tetrafluoropropanol and2,2,3,3,4,4,5,5-octafluoropentanol may be mentioned.

The temperature and the pressure in the polymerization of the compound(1) are not particularly limited. The polymerization temperature ispreferably from 0° C. to 200° C., particularly preferably from 25° C. to100° C. The polymerization pressure is preferably from the atmosphericpressure to 100 atm, particularly preferably from the atmosphericpressure to 10 atm.

The polymer of the present invention may be a homopolymer comprising therepeating units (U) alone or may be a copolymer containing the repeatingunits (U) and repeating units other than the repeating units (U). Thecopolymer is produced preferably by copolymerizing the compound (1) witha polymerizable compound other than the compound (1) (hereinafterreferred to as other compound).

Said other compound is not particularly limited so long as it is apolymerizable compound copolymerizable with the compound (1).

As said other compound, α-olefins such as ethylene, propylene andisobutylene; fluorinated olefins such as tetrafluoroethylene,hexafluoropropylene, perfluoro(2,2-dimethyl-1,3-dioxole andperfluoro(butenyl vinyl ether); after-mentioned hydrofluorodienes; vinylesters such as (meth)acrylic acid, a (meth)acrylate, vinyl acetate,vinyl benzoate and vinyl adamantate; vinyl ethers such as ethyl vinylether and cyclohexyl vinyl ether; cyclic olefins such as cyclohexene,norbornene and norbornadiene; maleic anhydride and vinyl chloride may bementioned. Here, (meth)acrylic acid means acrylic acid and methacrylicacid, and the (meth)acrylate means an acrylate and a methacrylate.

Said other compound is preferably a fluorodiene or a (meth)acrylate,particularly preferably C F₂═CF-Q^(M)-CH═CH₂, CH₂═CHC(O)OZ orCH₂═C(CH₃)C(O)OZ (wherein Q^(M) is —CF₂C(CF₃)(OZ)CH₂—,—CH₂CH(C(CF₃)₂(OZ)CH₂— or —CH₂CH(C(O)OZ)CH₂—). Further, Z is a hydrogenatom or a C₁₋₂₀ monovalent organic group as defined above.

The polymer of the present invention is a fluoropolymer containingrepeating units having a fluorinated alicyclic structure in its mainchain and having a carboxyl group or a group analogues thereto, derivedfrom the repeating units (U). The carboxyl groups or groups analoguesthereto in the repeating units may further be subjected to chemicalexchange to produce a polymer containing other repeating units.

For example, by blocking reaction of a polymer of the compound (1)wherein Z is a hydrogen atom with a blocking agent comprising analcohol, an alkyl halide and an alkoxyalkyl halide, a polymer havingcarboxyl groups in the above polymer blocked may be produced. Theblocking agent may be an alcohol selected from the group consisting ofHO—C(Y¹)₃, HO—CH₂OY² and the following compound, or an alkoxy halide ofthe alcohol.

Further, as the blocking agent, an alcohol having at least 20 carbonatoms, as represented by the following formula, or its halide may beused.

As specific examples of the blocking reaction, examples disclosed inHandbook of Reagents for Organic Synthesis: Activating Agents andProtecting Groups, edited by A. J. Pearson and W. R. Roush, John Wiley &Sons (1999) may be mentioned.

The compound (1) of the present invention is a compound having a highfluorine content as compared with a known cyclic polymerizable compoundhaving a group analogues to a carboxyl group(1,1,2-trifluoro-4-alkoxycarbonyl-1,6-heptadiene), and is considered tobe excellent in optical characteristics (such as transparency anddurable light resistance) and water and oil repellency. Further, a—C(CF₃)₂OH group can easily be introduced to obtain a compound havingboth water and oil repellency and solubility in a developer.Accordingly, the polymer of the present invention is a material usefulfor an application (e.g. a material for immersion lithography) whichrequires optical characteristics and water and oil repellency, oroptical characteristics, water and oil repellency and solubility in adeveloper.

EXAMPLES

Now, the present invention will be described in detail with reference toExamples. However, it should be understood that the present invention isby no means restricted thereto.

In Examples, tetrahydrofuran will be referred to as THF,dichloropentafluoropropane as R225, diisopropyl peroxydicarbonate asIPP, isopropyl alcohol as IPA, propylene glycol monomethyl ether acetateas PGMEA, tetramethylsilane as TMS, and1,1,2-trichloro-1,2,2-trifluoroethane as R113.

Further, the weight average molecular weight of the polymer will bereferred to as Mw, the number average molecular weight of the polymer asMn, and the glass transition temperature as Tg. Mw and Mn weredetermined by gel permeation chromatography (developing solvent: THF,internal standard: polystyrene). Tg was measured by differentialscanning calorimetry.

Example 1 Example for Preparation of Compound (1) Example 1-1 Examplefor Preparation of CF₂═CFCF₂C(C(O)OC(CH₃)₃)₂CH₂CH═CH₂ (HereinafterReferred to as a Compound (12¹))

In a reactor, NaH (2.1 g) with a purity of 60% and THF (100 mL) wereadded. CH₂(C(O)OC(CH₃)₃)₂ was dropwise added at 25° C. over a period of20 minutes with mixing and stirring. After completion of the dropwiseaddition, the content in the reactor was stirred at 25° C. as it was for100 minutes. Further, CH₂═CHCH₂Br (6.0 g) was added to the reactor overa period of 10 minutes, and the content in the reactor was stirred at65° C. for 5 hours. Then, water (100 mL) was added to the reactor toquench the reaction. The liquid in the reactor was subjected toextraction with 50 mL of tert-butyl methyl ether three times. Theextract was washed with a salt solution and then dried over sodiumsulfate. The extract was further concentrated and then distilled underreduced pressure to obtain CH₂═CHCH₂CH(C(O)OC(CH₃)₃)₂ (9.4 g) with a NMRpurity of 90%.

To the reactor, NaH (1.8 g) with a purity of 60% and THF (80 mL) wereput. To the reactor, CH₂═CHCH₂CH(C(O)OC(CH₃)₃)₂ (9.4 g) was dropwiseadded over a period of 15 minutes with mixing and stirring. At the timeof dropwise addition, the internal temperature of the reactor was keptat 20° C. or below. The content in the reactor was stirred at 25° C. asit is for 75 minutes.

Then, at an internal temperature of the reactor of 0° C., CF₂═CFCF₂OSO₂F(8.5 g) was added to the reactor over a period of 25 minutes. The liquidin the reactor was yellowed and a solid material (FSO₃Na) wasprecipitated. The content in the reactor was stirred as it was for 20hours. Water (150 mL) was added to the reactor to quench the reaction.

The solution in the reactor was subjected to extraction with tert-butylmethyl ether (50 mL) three times. The extract was washed with a sodiumchloride aqueous solution, dried over sodium sulfate and concentrated toobtain a crude product. The crude product was purified by silica gelcolumn chromatography to obtain a compound (12¹) (5.3 g).

The NMR data and IR data of the compound (12¹) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.47 (s,18H), 2.85 (d, J=6.9 Hz, 2H), 5.11 (dm, J=10.3 Hz, 1H), 5.18 (dm, J=17.1Hz, 1H), 5.90 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −95.2(ddt, J=36.4, 57.5, 4.7 Hz, 1F), −103.2 (ddd, J=4.7, 15.3, 29.3 Hz, 2F),−106.2 (ddt, J=57.5, 113.9, 29.3 Hz, 1F), −181.32 (ddt, J=36.4, 113.9,15.3 Hz, 1F).

IR (neat): 2982.2, 2935.9, 1786.3, 1740.6, 1641.7, 1370.9, 1349.8,1298.8, 1257.7, 1153.1, 1012.9, 912.2, 847.2 cm⁻¹.

Example 1-2 Example for Preparation of CF₂═CFCF₂C(C(O)OH)₂CH₂CH═CH₂(Hereinafter Referred to as Compound (12^(H)))

The compound (12¹) (6.4 g) was dropwise added to trifluoroacetic acid(60 mL) over a period of 5 minutes with stirring under cooling with ice,and after completion of the dropwise addition, stirring was continued asit was for 2 hours. Then, trifluoroacetic acid was distilled off underreduced pressure at 25° C. to obtain a compound (12^(H)) (4.6 g).

The NMR data and IR data of the compound (12^(H)) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 2.97 (d,J=7.3 Hz, 2H), 5.20 (dm, J=10.3 Hz, 1H), 5.26 (dm, J=17.1 Hz, 1H), 5.89(m, 1H), 11.29 (br, 2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −92.4(ddt, J=37.6, 54.0, 5.8 Hz, 1F), −102.6 (ddd, J=5.8, 15.3, 28.2 Hz, 2F),−105.1 (ddt, J=54.0, 115.0, 28.2 Hz, 1F), −183.0 (ddt, J=37.6, 115.0,15.3 Hz, 1F).

IR (neat): 3431.5, 3089.4, 2951.5, 1786.8, 1733.6, 1640.8, 1355.6,1302.5, 1217.0, 1185.5, 1135.3, 1080.9, 934.9, 910.1 cm⁻¹.

Example 1-3 Example for Preparation of CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂(Hereinafter Referred to as Compound (11^(H)))

The compound (12^(H)) (2.6 g) was mixed with toluene (15 mL), andtoluene was distilled off as it was, followed by heating at from 112 to139° C. for 1 hour. Further, drying under reduced pressure was carriedout to obtain a compound (11^(H)) (1.8 g).

The NMR data and IR data of the compound (11^(H)) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 2.55 (m, 1H),2.67 (m, 1H), 3.28 (m, 1H), 5.15 (m, 1H), 5.20 (m, 1H) 5.79 (m, 1H),11.72 (br, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −93.6(ddt, J=36.4, 58.7, 5.4 Hz, 1F), −105.4 (m, 2F), −108.0 (ddt, J=58.7,115.0, 29.3 Hz, 1F), −186.7 (ddt, J=36.4, 115.0, 15.3 Hz, 1F).

IR (neat) 3088.1, 2931.4, 1788.2, 1726.0, 1646.0, 1423.8, 1366.7,1309.0, 1257.8, 1171.9, 1067.2, 926.6 cm⁻¹.

Example 1-4 Example for Preparation ofCF₂═CFCF₂CH(C(O)OC(CH₃)₃)CH₂CH═CH₂ (Hereinafter Referred to as Compound(11¹))

The compound (11^(H)) is reacted with (CH₃)₂C═CH₂ under acidicconditions, whereby a compound (11¹) is obtained.

That is, to a reactor, the compound (11^(H)) (1.77 g) anddichloromethane (10 mL) were added, and three drops of concentratedsulfonic acid (about 0.04 g) were added. The content in the reactor wasstirred at 25° C., and CH₂═C(CH₃)₂ (0.51 g) was added to the reactorwith bubbling. The content in the reactor was stirred as it was for 5.5hours to carry out a reaction, and then a 5% sodium hydrogencarbonateaqueous solution (20 mL) was added to the reactor to quench thereaction. The solution in the reactor was subjected to extraction withtert-butyl methyl ether (50 mL) four times, and the obtained extract waswashed with a sodium chloride aqueous solution, dried over sodiumsulfate and concentrated. The obtained concentrated product was purifiedby silica gel column chromatography (developing solvent hexane:ethylacetate=10:1) to obtain a compound (11¹) (1.31 g).

The NMR data and IR data of the compound (11¹) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.45 (s, 9H),2.47 (m, 1H), 2.62 (m, 1H), 3.11 (m, 1H), 5.10 (m, 1H), 5.16 (m, 1H)5.76 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −95.0(ddt, J=36.4, 62.2, 5.9 Hz, 1F), −104.1 (dm, J=275.8 Hz, 1F), −107.7(dm, J=275.8 Hz, 1F), −108.9 (ddt, J=62.2, 115.0, 30.5 Hz, 1F), −186.0(ddt, J=36.4, 115.0, 15.3 Hz, 1F).

IR (neat) 2983.4, 2936.4, 1788.6, 1740.4, 1645.5, 1370.8, 1307.4,1254.1, 1159.4, 1112.5, 1064.9, 986.8, 926.4, 845.0 cm⁻¹.

Example 1-5 Example for Preparation ofCF₂═CFCF₂CH(C(O)OCH₂OCH₃)CH₂CH═CH₂ (Hereinafter Referred to as Compound(11²))

To a reactor, the compound (11^(H)) (2.30 g) and tert-butyl methyl ether(20 mL) were added, and diisopropylethylamine (1.29 g) was slowly added.Further, CH₃OCH₂Cl (0.79 g) was added, and the content in the reactorwas stirred as it was for 2 hours to carry out a reaction. Then, water(30 mL) was added to the reactor to quench the reaction, and an organiclayer was separated. The aqueous layer was subjected to extraction withtert-butyl methyl ether (10 mL) twice, and the extract was dried oversodium sulfate and concentrated to obtain a concentrated product, whichwas purified by silica gel column chromatography (developing solventhexane:ethyl acetate=5:1) to obtain a compound (11²) (1.97 g).

The NMR data and IR data of the compound (11²) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 2.53 (m, 1H),2.69 (m, 1H), 3.28 (m, 1H), 3.47 (s, 3H), 5.13 (dm, J=10.1 Hz, 1H), 5.19(dm, J=16.9 Hz, 1H), 5.28 (d, J=5.8 Hz, 1H), 5.31 (d, J=5.8 Hz, 1H),5.77 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −93.8(dddd, J=4.7, 5.9, 36.4, 59.9 Hz, 1F), −104.9 (dddt, J=5.9, 29.3, 277.0,15.3 Hz, 1F), −106.0 (dddt, J=4.7, 32.9, 277.0, 12.9 Hz, 1F), −108.2(dddd, J=29.3, 31.7, 59.9, 115.0 Hz, 1F), −186.6 (dddd, J=14.1, 15.3,36.4, 115.0 Hz, 1F).

IR (neat) 2964.7, 2836.1, 1788.6, 1752.1, 1645.6, 1351.2, 1308.3,1243.6, 1169.5, 1096.0, 930.3 cm⁻¹.

Example 1-6 Example for Preparation of Compound (11³)

To a solution containing the compound (11^(H)) (2.05 g) and tert-butylmethyl ether (20 mL), diisopropylethylamine (1.15 g) was slowly dropwiseadded under cooling with ice, and further, the following compound (w³)(1.91 g) was dropwise added. The solution was stirred as it was for 5hours to carry out a reaction. Then, water was added to the solution toquench the reaction, and an organic layer was recovered. The organiclayer was dried over magnesium sulfate and then concentrated to obtain acrude product. The crude product was purified by silica gel columnchromatography (developing solvent hexane:ethyl acetate=10:1) to obtainthe following compound (11³) (2.1 g).

The NMR data and IR data of the compound (113) are shown below.

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):1.51-1.97 (15H), 2.48-2.73 (2H), 3.22 (2H), 3.27 (1H) 5.13 (2H), 5.32(2H), 5.76 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −94.1 (1F), −105.3 (2F), −108.2 (1F), −186.4 (1F).

IR (neat) 2914.7, 2865.0, 1787.5, 1736.1, 1645.0, 1448.7, 1354.1,1307.7, 1246.9, 1188.3, 1170.5, 1103.1, 986.7, 925.9, 886.4, 840.1 cm⁻¹.

Example 1-7 Example for Preparation of Compound (11⁴)

To a solution containing the compound (11^(H)) (2.35 g) and toluene (3mL), two drops of concentrated sulfuric acid were added. Then, undercooling with ice, a toluene solution (3 mL) containing the followingcompound (w⁴) (2.04 g) was dropwise added to the solution to carry out areaction. The solution was stirred as it was for 12 hours, and then asodium hydrogencarbonate aqueous solution was added to the solution toquench the reaction, and an organic layer was recovered. The organiclayer was washed with water and dried over sodium sulfate and thenconcentrated to obtain a crude product. The crude product was purifiedby silica gel column chromatography (developing solvent hexane) toobtain the following compound (11⁴) (2.11 g).

The NMR data and IR data of the compound (11⁴) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.57 (m, 2H),1.59 (s, 3H), 1.69-1.92 (m, 8H), 2.02 (m, 2H), 2.29 (br, 2H), 2.49 (dm,J=14.6 Hz, 1H), 2.66 (dm, J=14.6 Hz, 1H), 3.19 (m, 1H), 5.11 (dm, J=10.1Hz, 1H), 5.18 (dm, J=17.1 Hz, 1H), 5.79 (ddt, J=10.1, 17.1, 6.9 Hz, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −94.6(dddd, J=4.7, 5.9, 35.2, 61.0 Hz, 1F), −104.4 (dm, J=275.8 Hz, 1F),−106.2 (dm, J=275.8 Hz, 1F), −108.6 (ddt, J=61.0, 115.0, 30.5 Hz, 1F),−185.9 (dddd, J=12.9, 15.3, 36.4, 116.2 Hz, 1F).

IR (neat) 2914.7, 2865.0, 1787.5, 1736.1, 1645.0, 1448.7, 1354.1,1307.7, 1246.9, 1188.3, 1170.5, 1103.1, 986.7, 925.9, 886.4, 840.1 cm⁻¹.

Example 1-8 Example for Preparation of Compound (11⁵)

To a solution containing the compound (11^(H)) (2.38 g) anddichloromethane (20 mL), a pyridinium salt (0.052 g) ofp-toluenesulfonic acid was added. Then, at 25° C., the followingcompound (w⁵) (1.60 g) was slowly added to the solution at 25° C.,followed by stirring as it was for 3.5 hours. The solution wasconcentrated, and the obtained crude product was purified by aluminacolumn chromatography (developing solvent hexane:ethyl acetate=10/1) toobtain the following compound (11⁵) (2.14 g).

The NMR data and IR data of the compound (11⁵) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.40-1.86 (m,6H), 2.54 (m, 1H), 2.70 (m, 1H), 3.27 (m, 1H), 3.72 (s, 1H), 3.86 (m,1H), 5.12 (dm, J=10.3 Hz, 1H), 5.18 (dm, J=17.1 Hz, 1H), 5.79 (ddt,J=6.6, 10.3, 17.1 Hz, 1H), 6.08 (s, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −93.7 to−94.2 (m, 1F), −104.1 to −106.8 (m, 2F), −107.8 to −108.7 (m, 1F),−186.0 to −186.9 (m, 1F).

IR (neat) 2951.7, 2877.4, 1788.2, 1749.9, 1644.7, 1357.9, 1307.6,1246.4, 1173.8, 1133.0, 1056.4, 1037.4, 937.0, 898.4, 860.9 cm⁻¹.

Example 1-9 Example for Preparation of Compound (11⁶)

To a solution containing the compound (11^(H)) (2.0 g) and tert-butylmethyl ether (20 mL), diisopropylethylamine (1.12 g) was slowly dropwiseadded under cooling with ice, and the following compound (w⁶) (1.83 g)was dropwise added as it was. The solution was stirred as it was for 5hours to carry out a reaction. Then, water was added to the solution toquench the reaction, and the organic layer was recovered. The organiclayer was dried over magnesium sulfate and concentrated to obtain acrude product. The crude product was purified by silica gel columnchromatography (developing solvent hexane:ethyl acetate=10:1) to obtainthe following compound (11⁶) (2.7 g).

The NMR data of the compound (11⁶) are shown below.

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):1.48-2.05 (15H), 2.47-2.73 (2H), 3.17-3.32 (1H), 5.08-5.21 (2H), 5.43(2H), 5.69-5.83 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −94.1 (1F), −105.9 (2F), −108.3 (1F), −186.4 (1F).

Example 1-10 Example for Preparation of Compound (11⁷)

To a reactor, the compound (11^(H)) (5.0 g), the following compound (w⁷)(9.9 g), dimethylaminopyridine (0.2 g) and dichloromethane (30 g) wereput and cooled to 0° C. Then, a solution having dicyclohexylcarbodiimide(4.7 g) dissolved in dichloromethane (15 g) was slowly dropwise added tothe reactor. The solution in the reactor was stirred as it was for 1hour to carry out a reaction, followed by stirring at 25° C. further for1 hour to carry out a reaction. The solution in the reactor wassubjected to filtration, and the filtrate was concentrated to obtain acrude product. The crude product was purified by silica gel columnchromatography (developing solvent hexane:ethyl acetate=20:1) to obtainthe following compound (11⁷) (10.5 g).

The NMR data of the compound (11⁷) is shown below.

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):2.64 to 2.70 (2H), 3.44 to 3.48 (1H), 5.16 to 5.21 (2H), 5.68 to −5.80(2H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −92.3 (1F), −105.2 (2F), −107.2 (1F), −123.6 (6F), −132.6 (2F),−187.3 (1F), −214.7 (m, 1F), −223.0 (1F).

The compound (w⁷) was prepared in accordance with the followingpreparation scheme (wherein, R^(f1)— is F(CF₂)₃OCF(CF₃)CF₂OCF(CF₃)—).

That is, to a flask in a nitrogen gas atmosphere (a compound (aw⁷) (15g), chloroform (100 g) and NaF (7.02 g) were put, and R^(f1)—COF (79 g)was dropwise added to the flask with stirring under cooling with ice,and the content in the flask was stirred. An insoluble solid material inthe flask was removed by pressure filtration, a saturated sodiumhydrogencarbonate aqueous solution (103 g) was put in the flask, and theorganic layer was recovered and concentrated to obtain a compound (bw⁷)(74 g).

R113 (313 g) was added to an autoclave provided with a NaF pellet-packedlayer at the gas outlet, nitrogen gas was blown to the autoclave for 1hour while the interior of the autoclave was stirred at 25° C., and thenfluorine gas diluted to 20 vol % with nitrogen gas was blown. While the20% fluorine gas was blown, a solution having a compound (bw⁷) (67 g)dissolved in R113 (299 g) was injected to the autoclave under a pressureof 0.1 MPa. After completion of the injection, the content in theautoclave was recovered and concentrated to obtain a compound (cw⁷).

The compound (cw⁷) (80 g) and powdery KF (0.7 g) were put in a flask ina nitrogen gas atmosphere, the flask was heated for 6 hours, and thenthe content in the flask was purified to obtain a compound (dw⁷) (38 g).

NaBH₄ (11 g) and THF (30 g) were put in a round-bottom flask in anitrogen gas atmosphere. While the flask was stirred under cooling withice, an R225 solution (48 g) containing 22 mass % of the compound (dw⁷)was dropwise added to the flask. After completion of the dropwiseaddition, the content in the flask was further stirred, and the solutionin the flask was neutralized with a 1N hydrochloric acid aqueoussolution (150 mL) to obtain a solution, which was washed with water andpurified by distillation to obtain a compound (w⁷).

The NMR data of the compound (w⁷) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 4.89 to 4.57(2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −105.0(1F), −119.7 (1F), −124.0 (1F), −124.3 (1F), −125.7 (1F), −126.8 (1F),−133.2 (2F), −216.6 (1F), −223.5 (1F).

Example 1-11 Example for Preparation ofCF₂═CFCF₂CH(C(O)OCH₂CF₂CF₃)CH₂CH═CH₂ (Hereinafter Referred to asCompound (11⁸))

To a reactor, the compound (11^(H)) (5.0 g), CF₃CF₂CH₂OH (3.6 g),dimethylaminopyridine (0.23 g) and dichloromethane (15 mL) were put andcooled to 0° C. Then, a solution having dicyclohexyl carbodiimide (4.9g) dissolved in dichloromethane (35 mL) was slowly dropwise added to thereactor. The solution in the reactor was stirred as it was for 1 hour tocarry out a reaction, and stirring was further carried out at 25° C. for1 hour to carry out a reaction.

Then, water was added to the reactor to quench the reaction, and anorganic layer was recovered. The organic layer was dried over magnesiumsulfate and concentrated to obtain a crude product. The crude productwas purified by silica gel column chromatography (developing solventhexane:ethyl acetate=10:1) to obtain a compound (11⁸) (4.0 g).

The NMR data of the compound (11⁸) are shown below.

¹H-NMR (300.4 MHz, solvent: deuterated acetone, standard: TMS) δ (ppm):2.51 to 2.73 (2H), 3.30 to 3.44 (1H), 4.50 to 4.69 (2H), 5.07-5.23 (2H),5.66 to 5.84 (1H).

¹⁹F-NMR (282.7 MHz, solvent: deuterated acetone, standard: CFCl₃) δ(ppm): −84.4 (3F), −94.2 (1F), −105.3 (2F), −107.8 (1F), −124.0 (2F),−187.0 (1F).

Example 1-12 Example for Preparation of Compound (11⁹)

Three drops of concentrated sulfonic acid were added to a solutioncontaining the compound (11^(H)) (7.6 g) and toluene (30 mL). Then,under cooling with ice, the following compound (w⁹) (4.1 g) was dropwiseadded to the solution to carry out a reaction. The temperature wasincreased to 25° C., and the solution was stirred as it was for 7 hours,and then a sodium hydrogencarbonate aqueous solution was added to thesolution to quench the reaction, and an organic layer was recovered. Theorganic layer was washed with water, dried over sodium sulfate andconcentrated to obtain a crude product. The crude product was purifiedby silica gel column chromatography (developing solvent hexane) toobtain the following compound (11⁹) (1.78 g).

The NMR data and IR data of the compound (11⁹) are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.57 (m, 2H),1.59 (s, 3H), 1.69-1.92 (m, 8H), 2.02 (m, 2H), 2.29 (br, 2H), 2.49 (dm,J=14.6 Hz, 1H), 2.66 (dm, J=14.6 Hz, 1H), 3.19 (m, 1H), 5.11 (dm, J=10.1Hz, 1H), 5.18 (dm, J=17.1 Hz, 1H), 5.79 (ddt, J=10.1, 17.1, 6.9 Hz, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −94.6(dddd, J=4.7, 5.9, 35.2, 61.0 Hz, 1F), −104.4 (dm, J=275.8 Hz, 1F),−106.2 (dm, J=275.8 Hz, 1F), −108.6 (ddt, J=61.0, 115.0, 30.5 Hz, 1F),−185.9 (dddd, J=12.9, 15.3, 36.4, 116.2 Hz, 1F).

IR (neat) 2914.7, 2865.0, 1787.5, 1736.1, 1645.0, 1448.7, 1354.1,1307.7, 1246.9, 1188.3, 1170.5, 1103.1, 986.7, 925.9, 886.4, 840.1 cm⁻¹.

Example 1-13 Example for Preparation ofCF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂ (Compound (11¹⁰))

To a reactor, the compound (11^(H)) (CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂) (1.5g), HO(CH₂)₃C(CF₃)₂OH (1.47 g) dimethylaminopyridine (0.07 g) anddichloromethane (20 g) were put and cooled to 0° C. Then, a 1Mdichloromethane solution (9.04 g) of dicyclohexylcarbodiimide was slowlydropwise added to the reactor. The solution in the reactor was stirredat 25° C. for 1 hour to carry out a reaction. The solution in thereactor was subjected to filtration, and the filtrate was concentratedto obtain a crude product. The crude product was purified by silica gelcolumn chromatography (developing solvent hexane:ethyl acetate=15:1) toobtain CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂ (2.4 g) (compound11¹⁰)).

The NMR data are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.85 to 2.04(m, 4H), 2.49 to 2.69 (m, 2H), 3.20 to 3.33 (m, 1H), 3.37 (S, 1H), 4.19to 4.23 (m, 2H), 5.10 to 5.19 (m, 2H), 5.67 to 5.80 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −77.0 to−78.1 (m, 6F), −93.5 to −93.9 (m, 1F), −104.6 to −106.7 (m, 2F), −107.8to −108.6 (m, 1F), −186.3 to −186.9 (m, 1F).

Example 1-14 Example for Preparation ofCF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂ (Compound (11¹¹))

To a reactor, the compound (11^(H)) (CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂) (1.0g), OHCH(CH₃)CH₂C(CF₃)₂OH (0.98 g), dimethylaminopyridine (0.07 g) andtoluene (20 g) were put and cooled to 0° C. Then, a solution havingdicyclohexylcarbodiimide (1.11 g) dissolved in toluene (6 g) was slowlydropwise added to the reactor. The solution in the reactor was stirredat 25° C. for 1 hour, followed by stirring at 40° C. for 3 hours, andstirring was carried out at 70° C. further for 2 hours to carry out areaction. The solution in the reactor was subjected to filtration, andthe filtrate was concentrated to obtain a crude product. The crudeproduct was purified by silica gel column chromatography (developingsolvent hexane:ethyl acetate=25:1) to obtainCF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂ (1.14 g) (compound(11¹¹)).

The NMR data are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 1.26 to 1.43(m, 3H), 2.21 to 2.26 (m, 2H), 2.50 to 2.70 (m, 2H), 3.19 to 3.31 (m,1H), 4.84 to 4.87 (m, 1H), 5.13 to 5.25 (m, 3H), 5.67 to 5.77 (m, 1H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −76.5 to−79.6 (md, J=627.8, 6F), −92.9 to −93.3 (m, 1F), −103.2 to −108.1 (m,3F), −186.4 to −187.1 (m, 1F).

Example 1-15 Example for Preparation ofCF₂═CFCF₂CH(C(O)OCH(CH₂C(CF₃)₂OH)₂)CH₂CH═CH₂ (Compound (11¹²))

To a reactor, the compound (11^(H)) (CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂) (1.0g), OHCH(CH₂C(CF₃)₂OH)₂ (1.7 g), dimethylaminopyridine (0.14 g),dichloromethane (10 g) and toluene (30 g) were put and cooled to 0° C.Then, a 1M dichloromethane solution (6.03 g) of dicyclohexylcarbodiimidewas slowly dropwise added to the reactor. The solution in the reactorwas stirred at 25° C. for 2 hours to carry out a reaction. The solutionin the reactor was subjected to filtration, and the filtrate wasconcentrate to obtain a crude product. The crude product was purified bysilica gel column chromatography (developing solvent hexane:ethylacetate=20:1) to obtain CF₂═CFCF₂CH(C(O)OCH(CH₂C(CF₃)₂OH)₂)CH₂CH═CH₂(1.13 g) (compound (11¹²)).

The NMR data are shown below.

¹H-NMR (300.4 MHz, solvent: CDCl₃, standard: TMS) δ (ppm): 2.31 to 2.41(m, 2H), 2.59 to 2.73 (m, 4H), 3.37 to 3.51 (m, 1H), 5.06 to 5.22 (m,2H), 5.70 to 5.90 (m, 2H), 7.09 (s, 2H).

¹⁹F-NMR (282.7 MHz, solvent: CDCl₃, standard: CFCl₃) δ (ppm): −75.5 to−78.6 (m d, J=239.8, 12F), −93.9 to −95.1 (m, 1F), −103.2 to −105.5 (m,2F), −107.5 to −108.4 (m, 1F), −185.8 to −186.5 (m, 1F).

Example 2 Example for Preparation of Polymer Example 2-1 Example forPreparation of Polymer (1)

To a pressure resistant reactor (internal capacity: 30 mL, made ofglass), the compound (12¹) (1.51 g) and ethyl acetate (3.41 g) werecharged. Then, an R225 solution (0.20 g) containing 50 mass % of IPP asa polymerization initiator was added to the pressure resistant reactor.The reactor was freeze-deaerated, and polymerization was carried out for18 hours while the reactor was kept at 40° C. The solution in thereactor was dropwise added to methanol, and the formed solid materialwas recovered and vacuum-dried at 80° C. for 20 hours to obtain apolymer (1) (0.84 g) as a white powder at 25° C.

Of the polymer (1), Mw was 6,300 and Mn was 4,600.

Further, as a result of analyzing the polymer (1) by ¹⁹F-NMR and ¹H-NMR,the polymer (1) was confirmed to contain at least one type of repeatingunits (U12¹) selected from the group consisting of repeating unitsrepresented by the following formulae (U1-12¹), (U2-12¹) and (U3-12¹).

The polymer (1) was soluble in acetone, THF, ethyl acetate, methanol and2-perfluorohexyl ethanol, and insoluble in R225,perfluoro(2-butyltetrahydrofuran) and perfluoro-n-octane.

Example 2-2 Example for Preparation of Polymer (2)

To a pressure resistant reactor (internal capacity: 20 mL, made ofglass), the compound (12^(H)) (1.00 g), R225 (5.41 g) and IPP (0.10 g)were charged. Then, an R225 solution (0.28 g) containing 50 mass % ofIPP was added to the pressure resistant reactor as a polymerizationinitiator. The reactor was freeze-deaerated, and polymerization wascarried out for 18 hours while the reactor was kept at 40° C. Thesolvent in the reactor was changed to THF, and the solution was dropwiseadded to hexane, and the formed solid material was recovered andvacuum-dried at 80° C. for 20 hours to obtain a polymer (2) (0.82 g) asa white powder at 25° C.

Of the polymer (2), Mw was 22,100 and Mn was 8,700.

Further, as a result of analyzing the polymer (2) by ¹⁹F-NMR and ¹H-NMR,the polymer (2) was confirmed to contain at least one type of repeatingunits (U12^(H)) selected from the group consisting of repeating unitsrepresented by the following formulae (U1-12^(H)), (U2-12^(H)) and(U3-12^(H)).

When the polymer (2), sodium hydroxide and CH₃OCH₂Cl are reacted inmethanol, a polymer containing any one type of repeating unitsrepresented by the following formulae is obtained.

Example 2-3 Example for Preparation of Polymer (3)

To a reactor (internal capacity: 200 mL, made of glass), the compound(11^(H)) (16.0 g) and ethyl acetate (129.8 g) were charged, and as apolymerization initiator, IPP (5.95 g) as a 50 mass % R225 solution wasadded. The reactor was deaerated under reduced pressure, andpolymerization reaction was carried out at an internal temperature ofthe reactor of 40° C. for 18 hours. The solution in the reactor wasdropwise added to hexane, and the obtained solid material was recoveredand vacuum-dried at 120° C. for 40 hours to obtain a polymer (3) (15.5g) as a white powder at 25° C.

Of the polymer (3), Mw was 9,700 and Mn was 4,600, and Tg was 178° C.Further, as a result of analyzing the polymer (3) by ¹⁹F-NMR and ¹H-NMR,the polymer (3) was confirmed to contain at least one type of repeatingunits (U11^(H)) selected from the group consisting of repeating unitsrepresented by the following formulae (U1-11^(H)), (U2-11^(H)) and(U3-11^(H)).

The polymer (3) was soluble in acetone, THF, ethyl acetate, methanol andPGMEA, and insoluble in R225, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 2-4 Example for Preparation of Polymer (4)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11¹) (0.8 g), R225 (8.0 g) and IPA (0.06 g) were charged, and as apolymerization initiator, IPP (1.0 g) as a 50 mass % R225 solution wasadded. The reactor was deaerated under reduced pressure, andpolymerization reaction was carried out at an internal temperature ofthe reactor of 40° C. for 18 hours. The solution in the reactor wasdropwise added to hexane (90 g), and the obtained solid material wasrecovered and vacuum-dried at 90° C. for 40 hours to obtain a polymer(4) (0.56 g) as a white powder at 25° C.

Of the polymer (4), Mw was 16,000 and Mn was 11,000, and Tg was 118° C.Further, as a result of analyzing the polymer (4) by ¹⁹F-NMR and ¹H-NMR,the polymer (4) was confirmed to contain at least one type of repeatingunits (U11¹) selected from the group consisting of repeating unitsrepresented by the following formulae (U1-11¹), (U2-11¹) and (U3-11¹).

The polymer (4) was soluble in acetone, THF, ethyl acetate and PGMEA,and insoluble in R225, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 2-5 Example for Preparation of Polymer (5)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11²) (0.8 g), R225 (4.3 g) and IPA (0.07 g) were charged, and as apolymerization initiator, IPP (0.53 g) as a 50 mass % R225 solution wasadded. The reactor was deaerated under reduced pressure, andpolymerization reaction was carried out at an internal temperature ofthe reactor of 40° C. for 18 hours. The solution in the reactor wasdropwise added to hexane (60 g), and the obtained solid material wasrecovered and vacuum-dried at 90° C. for 40 hours to obtain a polymer(5) (0.6 g) as a white powder at 25° C.

Of the polymer (5), Mw was 15,800 and Mn was 8,900.

By NMR analysis, the polymer (5) was confirmed to contain at least onetype of repeating units (U11²) selected from the group consisting ofrepeating units represented by the following formulae (U1-11²), (U2-11²)and (U3-11²).

The polymer (5) was soluble in acetone, THF, ethyl acetate and PGMEA,and insoluble in R225, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 2-6 Example for Preparation of Polymer (6)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11³) (2.0 g) and ethyl acetate (15.8 g) were charged, IPP (0.73 g) as a50 mass % R225 solution was charged, and a polymerization reaction wascarried out at 40° C. for 18 hours. The solution in the reactor wasdropwise added to hexane, and the obtained solid material was recoveredand vacuum-dried at 90° C. for 24 hours to obtain a polymer (6) (1.40g).

Of the polymer (6), Mw was 12,600 and Mn was 6,100, and Tg was 90° C. ByNMR analysis, the polymer (6) was confirmed to contain at least one typeof repeating units (U11³) selected from the group consisting ofrepeating units represented by the following formulae (U1-11³), (U2-11³)and (U3-11³).

The polymer (6) was in the form of a white powder at 25° C., and solublein acetone, tetrahydrofuran and ethyl acetate.

Example 2-7 Example for Preparation of Polymer (7)

To a reactor (internal capacity: 30 mL), the compound (11⁴) (2.0 g) andethyl acetate (11.0 g) were charged, IPP (0.53 g) as a 50 mass % R225solution was charged, and a polymerization reaction was carried out at40° C. for 18 hours. The solution in the reactor was dropwise added tohexane, and the obtained solid material was recovered and vacuum-driedat 110° C. for 24 hours to obtain a polymer (7) (1.90 g).

Of the polymer (7), Mw was 23,500 and Mn was 9,600, and Tg was 161° C.

By NMR analysis, the polymer (7) was confirmed to contain at least onetype of repeating units (U11⁴) selected from the group consisting ofrepeating units represented by the following formulae (U1-11⁴), (U2-11⁴)and (U3-11⁴).

The polymer (7) was in the form of a white powder at 25° C., and solublein tetrahydrofuran and ethyl acetate.

Example 2-8 Example for Preparation of Polymer (8)

To a reactor (internal capacity: 30 mL), the compound (11⁶) (1.0 g) andethyl acetate (8.8 g) were charged, IPP (0.40 g) as a 50 mass % R225solution was charged, and a polymerization reaction was carried out at40° C. for 18 hours. The solution in the reactor was dropwise added tomethanol, and the obtained solid material was recovered and vacuum-driedat 90° C. for 24 hours to obtain a polymer (8) (0.62 g).

Of the polymer (8), Mn was 6,100 and Mw was 10,200, and Tg was 107° C.By NMR analysis, the polymer (8) was confirmed to contain at least onetype of repeating units (U11⁶) selected from the group consisting ofrepeating units represented by the following formulae (U1-11⁶), (U2-11⁶)and (U3-11⁶).

Example 2-9 Example for Preparation of Polymer (9)

To a reactor (internal capacity: 30 mL), the compound (11⁷) (0.5 g) andR225 (1.93 g) were charged, IPP (0.15 g) as a 50 mass % R225 solutionwas charged, and a polymerization reaction was carried out at 40° C. for18 hours. The solution in the reactor was dropwise added to hexane, andthe obtained solid material was recovered and vacuum-dried at 100° C.for 24 hours to obtain a polymer (9) (0.42 g).

Of the polymer (9), Mn was 9,900 and Mw was 15,100.

By NMR analysis, the polymer (9) was confirmed to contain at least onetype of repeating units (U11⁷) selected from the group consisting ofrepeating units represented by the following formulae (U1-11⁷), (U2-11⁷)and (U3-11⁷).

The polymer (9) was in the form of a white powder at 25° C., and solublein acetone, THF, methanol and R225.

Example 2-10 Example for Preparation of Polymer (10)

To a reactor (internal capacity: 30 mL), the compound (11⁸) (0.81 g) andR225 (7.2 g) were charged, IPP (0.81 g) as a 50 mass % R225 solution wascharged, and a polymerization reaction was carried out at 40° C. for 18hours. The solution in the reactor was dropwise added to hexane, and theobtained solid material was recovered and vacuum-dried at 90° C. for 24hours to obtain a polymer (10) (0.66 g).

Of the polymer (10), Mn was 4,300 and Mw was 6,600.

By NMR analysis, the polymer (10) was confirmed to contain at least onetype of repeating units (U11⁸) selected from the group consisting ofrepeating units represented by the following formulae (U1-11⁸), (U2-11⁸)and (U3-11⁸).

Example 2-11 Example for Preparation of Polymer (11)

To a reactor (internal capacity: 30 mL), the compound (11⁹) (0.89 g) andethyl acetate (7.8 g) were charged, IPP (0.35 g) as a 50 mass % R225solution was charged, and a polymerization reaction was carried out at40° C. for 18 hours. The solution in the reactor was dropwise added tohexane, and the obtained solid material was recovered and vacuum-driedat 90° C. for 24 hours to obtain a polymer (11) (0.80 g).

Of the polymer (11), Mn was 7,500 and Mw was 16,000.

By NMR analysis, the polymer (11) was confirmed to contain at least onetype of repeating units (U11⁹) selected from the group consisting ofrepeating units represented by the following formulae (U1-11⁹), (U2-11⁹)and (U3-11⁹).

The polymer (11) was in the form of a white powder at 25° C., andsoluble in tetrahydrofuran and ethyl acetate.

Example 2-12 Example for Preparation of Polymer (12)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11^(H)) (0.67 g), the compound (11²) (2.8 g) and ethyl acetate (22.7 g)were charged, and as a polymerization initiator, IPP (1.1 g) as a 50mass % R225 solution was added. The reactor was deaerated under reducedpressure, and a polymerization reaction was carried out at an internaltemperature of the reactor of 40° C. for 18 hours. The solution in thereactor was dropwise added to hexane (270 g), and the obtained solidmaterial was recovered and vacuum-dried at 110° C. for 40 hours toobtain a polymer (12) (2.55 g) as a white powder at 25° C.

Of the polymer (12), Mw was 15,400, and Mn was 8,300.

By NMR analysis, the polymer (12) was confirmed to be a polymercontaining repeating units (U11^(H)) and repeating units (U11²) and tocontain 36 mol % of the repeating units (U11^(H)) and 64 mol % of therepeating units (U11²) based on all the repeating units.

The polymer (12) was soluble in acetone, THF, ethyl acetate, methanoland PGMEA, and insoluble in R225, perfluoro(2-butyltetrahydrofuran) andperfluoro-n-octane.

Example 2-13 Example for Preparation of Polymer (13)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11^(H)) (0.07 g), the compound (11¹) (0.75 g) and ethyl acetate (1.85g) were charged, and as a polymerization initiator, IPP (0.11 g) as a 50mass % R225 solution was added. The reactor was deaerated under reducedpressure, and a polymerization reaction was carried out at an internaltemperature of the reactor of 40° C. for 18 hours. The solution in thereactor was dropwise added to hexane, and the obtained solid materialwas recovered and vacuum-dried at 90° C. for 24 hours to obtain apolymer (13) (0.67 g).

Of the polymer (13), Mw was 28,000, and Mn was 14,500.

By NMR analysis, the polymer (13) was confirmed to be a polymercontaining repeating units (U11^(H)) and repeating units (U11¹) and tocontain 12 mol % of the repeating units (U11^(H)) and 88 mol % of therepeating units (U11¹) based on all the repeating units.

Example 2-14 Example for Preparation of Polymer (14)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11⁴) (0.75 g), the compound (11⁸) (0.18 g) and ethyl acetate (6.7 g)were charged, and as a polymerization initiator, IPP (0.31 g) as a 50mass % R225 solution was added. The reactor was deaerated under reducedpressure, and a polymerization reaction was carried out at an internaltemperature of the reactor of 40° C. for 18 hours. The solution in thereactor was dropwise added to hexane, and the obtained solid materialwas recovered and vacuum-dried at 90° C. for 24 hours to obtain apolymer (14) (0.61 g).

Of the polymer (14), Mw was 18,900, and Mn was 10,600.

By NMR analysis, the polymer (14) was confirmed to be a polymercontaining repeating units (U11⁴) and repeating units (U11⁸) and tocontain 77 mol % of the repeating units (U11⁴) and 23 mol % of therepeating units (U11⁸) based on all the repeating units.

Example 2-15 Example for Preparation of Polymer (15)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11^(H)) (0.20 g), the compound (11⁷) (0.45 g) and ethyl acetate (5.7 g)were charged, and as a polymerization initiator, IPP (0.26 g) as a 50mass % R225 solution was added. The reactor was deaerated under reducedpressure, and a polymerization reaction was carried out at an internaltemperature of the reactor of 40° C. for 18 hours. The solution in thereactor was dropwise added to hexane, and the obtained solid materialwas recovered and vacuum-dried at 100° C. for 24 hours to obtain apolymer (15) (0.51 g).

Of the polymer (15), Mw was 15,400, and Mn was 8,300.

As a result of analyzing the polymer (15) by NMR, the polymer (15) wasconfirmed to be a polymer containing repeating units (U11^(H)) andrepeating units (U11⁷) and to contain 52 mol % of the repeating units(U11^(H)) and 48 mol % of the repeating units (U11⁷) based on all therepeating units. Further, the polymer (15) was soluble in acetone, THF,ethyl acetate and methanol.

Example 2-16 Example for Preparation of Polymer (16)

To a pressure resistant reactor (internal capacity: 30 mL, made ofglass), a compound (CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂)(compound (11¹⁰)) (1.0 g) and ethyl acetate (7.0 g) were charged. Then,an R225 solution (0.67 g) containing 50 mass % of IPP was added as apolymerization initiator to the pressure resistant reactor. The reactorwas freeze-deaerated, and polymerization was carried out for 18 hourswhile the reactor was kept at 40° C. The solution in the reactor wasdropwise added to hexane, and the formed solid material was recoveredand vacuum-dried at 80° C. for 18 hours to obtain a polymer (16) (1.64g) as a white powder at 25° C.

Of the polymer (16), Mw was 9,700, and Mn was 5,800.

Further, as a result of analyzing the polymer (16) by ¹⁹F-NMR and¹H-NMR, the polymer (16) was confirmed to contain at least one type ofrepeating units (U11¹⁰) selected from the group consisting of repeatingunits represented by the following formulae (U1-11¹⁰), (U2-11¹⁰) and(U3-11¹⁰).

The polymer (16) was soluble in acetone, THF, ethyl acetate andmethanol.

Example 2-17 Example for Preparation of Polymer (17)

To a pressure resistant reactor (internal capacity: 30 mL, made ofglass), a compound (CF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂)(compound (11¹¹)) (0.8 g) and ethyl acetate (3.6 g) were charged. Then,an R225 solution (0.363 g) containing 50 mass % of IPP was added as apolymerization initiator to the pressure resistant reactor. The reactorwas freeze-deaerated, and polymerization was carried out for 18 hourswhile the reactor was kept at 40° C. The solution in the reactor wasdropwise added to hexane, and the formed solid material was recoveredand vacuum-dried at 80° C. for 24 hours to obtain a polymer (17) (0.4 g)as a white powder at 25° C.

Of the polymer (17), Mw was 9,000, and Mn was 6,000.

Further, as a result of analyzing the polymer (17) by ¹⁹F-NMR and¹H-NMR, the polymer (16) was confirmed to contain at least one type ofrepeating units (U11¹¹) selected from the group consisting of repeatingunits represented by the following formulae (U1-11¹¹), (U2-11¹¹) and(U3-11¹¹).

The polymer (17) was soluble in acetone, THF, ethyl acetate andmethanol.

Example 2-18 Example for Preparation of Polymer (18)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11^(H)) (CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂) (0.10 g), a compound(CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂) (0.52 g) and ethyl acetate(4.9 g) were charged, and IPP (0.22 g) as a 50 mass % R225 solution wasadded as a polymerization initiator. The reactor was deaerated underreduced pressure, and a polymerization reaction was carried out at aninternal temperature of the reactor of 40° C. for 18 hours. The solutionin the reactor was dropwise added to hexane, and the obtained solidmaterial was recovered and vacuum-dried at 90° C. for 24 hours to obtaina polymer (18) (0.45 g).

Of the polymer (18), Mw was 11,900, and Mn was 6,400.

As a result of analyzing the polymer (18) by NMR, the polymer (18) wasconfirmed to be a polymer containing the repeating units (U11H) andrepeating units (CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂), and to bea polymer containing 23 mol % of the repeating units (U11^(H)) and 77mol % of the repeating units(CF₂═CFCF₂CH(C(O)O(CH₂)₃C(CF₃)₂OH)CH₂CH═CH₂) based on all the repeatingunits. Further, the polymer (18) was soluble in acetone, THF, ethylacetate and methanol.

Example 2-19 Example for Preparation of Polymer (19)

To a reactor (internal capacity: 30 mL, made of glass), the compound(11^(H)) (CF₂═CFCF₂CH(C(O)OH)CH₂CH═CH₂) (0.10 g), a compound(CF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂) (0.44 g) and ethylacetate (4.8 g) were charged, and IPP (0.22 g) as a 50 mass % R225solution was added as a polymerization initiator. The reactor wasdeaerated under reduced pressure, and a polymerization reaction wascarried out at an internal temperature of the reactor of 40° C. for 18hours. The solution in the reactor was dropwise added to hexane, and theobtained solid material was recovered and vacuum-dried at 90° C. for 24hours to obtain a polymer (19) (0.39 g).

Of the polymer (19), Mw was 11,600, and Mn was 6,500.

As a result of analyzing the polymer (19) by NMR, the polymer (19) wasconfirmed to be a polymer containing the repeating units (U11^(H)) andrepeating units (CF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂), and tobe a polymer containing 28 mol % of the repeating units (U11^(H)) and 72mol % of the repeating units(CF₂═CFCF₂CH(C(O)OCH(CH₃)CH₂C(CF₃)₂OH)CH₂CH═CH₂) based on all therepeating units. Further, the polymer (19) was soluble in acetone, THF,ethyl acetate and methanol.

Example 2-20 Example for Preparation of Polymer (20)

To a pressure resistant reactor (internal capacity: 30 mL, made ofglass), a compound (CF₂═CFCF₂CH(C(O)OCH(CH₂C(CF₃)₂OH)₂)CH₂CH═CH₂)(compound (11¹²)) (0.5 g) and ethyl acetate (4.4 g) were charged. Then,an R225 solution (0.2 g) containing 50 mass % of IPP was added as apolymerization initiator to the pressure resistant reactor. The reactorwas freeze-deaerated, and polymerization was carried out for 18 hourswhile the reactor was kept at 40° C. The solution in the reactor wasdropwise added to hexane, and the formed solid material was recoveredand vacuum-dried at 90° C. for 24 hours to obtain a polymer (20) (0.28g) as a white powder at 25° C.

Of the polymer (20), Mw was 10,300, and Mn was 6,800.

Further, as a result of analyzing the polymer (20) by ¹⁹F-NMR and¹H-NMR, the polymer (20) was confirmed to contain at least one type ofrepeating units (U11¹²) selected from the group consisting of repeatingunits represented by the following formulae (U1-11¹²), (U2-11¹²) and(U3-11¹²).

The polymer (20) was soluble in acetone, THF, ethyl acetate andmethanol.

Example 3 Evaluation Example of Water Repellency of Polymer

The polymer (1) was dissolved in PGMEA to prepare a PGMEA solutioncontaining 10 mass % of the polymer (1), and the solution was filtratedthrough a filter (made of polytetrafluoroethylene, pore size: 0.2 μm) toobtain a resin solution.

Then, a silicon substrate having an antireflection film (manufactured byROHM AND HAAS Electronic Materials, tradename: AR26) on its surface, wasspin-coated with the resin solution, and the silicon substrate washeat-treated at 100° C. for 90 seconds to obtain a resin thin filmcomprising the polymer (1) on the silicon substrate. Then, the staticcontact angle, the sliding angle, the advancing angle and the recedingangle of the resin thin film to water were measured. For themeasurement, a contact angle meter DM-700 manufactured by KyowaInterface Science Co., Ltd. was used. Further, the volume of water dropsused was 2 μL in the case of the contact angle, and 50 μL in the case ofthe sliding angle, the advancing angle and the receding angle. Further,the sliding angle measured by means of a sliding method will be referredto as “sliding angle”, the advancing contact angle will be referred toas “advancing angle”, and the receding contact angle will be referred toas “receding angle”. The units of the static contact angle, the slidingangle, the advancing angle and the receding angle were degree (°).

Further, the static contact angle, the sliding angle, the advancingangle and the receding angle were measured in the same manner exceptthat the polymer (4) or (5) was used instead of the polymer (1). Theresults are summarized in Table 1.

TABLE 1 Material for forming a Static Sliding Advancing Receding resinthin film contact angle angle angle angle Polymer (1) 86 9 89 79 Polymer(4) 88 8 91 83 Polymer (5) 75 21 81 61

Further, resin thin films were formed in the same method except that asolution containing each of the polymers (2), (3), (6) to (11), (13),(14) and (15) was used instead of the PGMEA solution containing 10 mass% of the polymer (1), and the static contact angle, the sliding angle,the advancing angle and the receding angle were measured. Further, withrespect to the polymers (16) to (20), a solution containing a4-methyl-2-pentanol solution containing 4 mass % of each of the polymers(16) to (20) was used. The results are summarized in Table 2.

TABLE 2 Material for forming a Static Sliding Advancing Receding resinthin film contact angle angle angle angle Polymer (2) 54 48 70 23Polymer (3) 56 44 67 21 Polymer (6) 86 14 89 75 Polymer (7) 87 8 87 80Polymer (8) 82 14 86 73 Polymer (9) 103 12 105 92 Polymer (10) 98 15 8673 Polymer (11) 86 9 90 80 Polymer (13) 86 14 89 75 Polymer (14) 89 1292 80 Polymer (15) 96 50 101 53 Polymer (16) 74 19 82 63 Polymer (17) 8015 84 69 Polymer (18) 71 24 77 55 Polymer (19) 75 23 81 59 Polymer (20)73 17 79 62

As evident from the above results, the polymer of the compound (1) ofthe present invention is useful as a water repellent material to form acoating film excellent in water and oil repellency.

INDUSTRIAL APPLICABILITY

The polymer of the present invention is useful as a resist material forlithography (particularly a photosensitive resist material for immersionlithography, a resist protective film material for immersionlithography), a material for an ion exchange membrane, a material forfuel cells, an optical fiber material, electronic components, atransparent resin film material, an adhesive material, a fiber material,a material for a weather resistant coating material, etc.

The entire disclosures of Japanese Patent Application No. 2007-093221filed on Mar. 30, 2007 and Japanese Patent Application No. 2007-261185filed on Oct. 4, 2007 including specifications, claims, drawings andsummaries are incorporated herein by reference in their entireties.

1. A compound represented by the following formula (1):CF₂═CFCF₂C(X)(C(O)OZ)(CH₂)_(n)CR═CHR  (1) wherein X is a hydrogen atom,a cyano group or a group represented by the formula —C(O)OZ; Z is ahydrogen atom or a C₁₋₂₀ monovalent organic group; n is 0, 1 or 2; and Ris a hydrogen atom or a C₁₋₂₀ monovalent organic group, provided thattwo R's may be the same or different.
 2. A compound represented by thefollowing formula (11):CF₂═CFCF₂CH(C(O)OZ¹)CH₂CH═CH₂  (11) wherein Z¹ is a hydrogen atom, agroup represented by the formula —C(Y¹)₃, a group represented by theformula —CH₂OY² or a group represented by the following formula:

each of Y¹ and Y² which are independent of each other, is a hydrogenatom or a C₁₋₁₉ monovalent saturated hydrocarbon group; Y³ is a hydrogenatom or a C₁₋₁₆ monovalent saturated hydrocarbon group; and Q³ is aC₃₋₁₉ group which forms a bivalent cyclic hydrocarbon group incombination with the carbon atom in the formula, provided that in Y¹, Y²and Y³ in the case of a monovalent saturated hydrocarbon group and Q³,between the carbon atom-carbon atom, a group represented by the formula—O—, a group represented by the formula —C(O)— or a group represented bythe formula —C(O)O— may be inserted, and to a carbon atom in Y¹, Y², Y³and Q³, a fluorine atom, a hydroxyl group or a carboxyl group may bebonded.
 3. A compound represented by the following formula (111):CF₂═CFCF₂CH(C(O)OZ¹¹)CH₂CH═CH₂  (111) wherein Z¹¹ is a hydrogen atom, agroup represented by the formula —C(Y¹¹)₃, a group represented by theformula —CH₂OY²¹ or a group represented by the formula:

Y¹¹ is a C₁₋₆ monovalent saturated hydrocarbon group, Y²¹ is a C₁₋₁₂monovalent saturated hydrocarbon group or a C₂₋₁₂ monovalent saturatedhydrocarbon group containing a group represented by the formula —O—; Y³¹is a hydrogen atom or a C₁₋₆ monovalent saturated hydrocarbon group; andQ³¹ is a C₄₋₁₂ a bivalent saturated hydrocarbon group, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent saturatedhydrocarbon group having a group represented by the formula —O—, a grouprepresented by the formula —C(O)— or a group represented by the formula—C(O)O— inserted between the carbon atom-carbon atom.
 4. A compoundrepresented by the following formula (1111):CF₂═CFCF₂CH(C(O)OZ¹¹¹)CH₂CH═CH₂  (1111) wherein Z¹¹¹ is a C₃₋₂₀monovalent organic group having at least one group represented by theformula —C(CF₃)₂OH.
 5. A compound represented by the following formula(12):CF₂═CFCF₂C(C(O)OZ¹)₂CH₂CH═CH₂  (12) wherein Z¹ is a hydrogen atom, agroup represented by the formula —C(Y¹)₃, a group represented by theformula —CH₂OY² or a group represented by the following formula:

each of Y¹ and Y² which are independent of each other, is a hydrogenatom or a C₁₋₁₉ monovalent saturated hydrocarbon group; Y³ is a hydrogenatom or a C₁₋₆ monovalent saturated hydrocarbon group; and Q³ is a C₃₋₁₉group which forms a bivalent cyclic hydrocarbon group in combinationwith the carbon atom in the formula, provided that in Y¹, Y² and Y³ inthe case of a monovalent saturated hydrocarbon group and Q³, between thecarbon atom-carbon atom, a group represented by the formula —O—, a grouprepresented by the formula —C(O)— or a group represented by the formula—C(O)O— may be inserted, and to a carbon atom in Y¹, Y², Y³ and Q³, afluorine atom, a hydroxyl group or a carboxyl group may be bonded.
 6. Acompound represented by the following formula (121):CF₂═CFCF₂C(C(O)OZ¹¹)₂CH₂CH═CH₂  (121) wherein Z¹¹ is a hydrogen atom, agroup represented by the formula —C(Y¹¹)₃, a group represented by theformula —CH₂OY²¹ or a group represented by the following formula:

Y¹¹ is a C₁₋₆ monovalent saturated hydrocarbon group; Y²¹ is a C₁₋₁₂monovalent saturated hydrocarbon group or a C₂₋₁₂ monovalent saturatedhydrocarbon group containing a group represented by the formula —O—; Y³¹is a hydrogen atom or a C₁₋₆ monovalent saturated hydrocarbon group; andQ³¹ is a C₄₋₁₂ a bivalent saturated hydrocarbon group, a C₄₋₁₂ bivalentfluorinated saturated hydrocarbon group or a C₄₋₁₂ bivalent saturatedhydrocarbon group having a group represented by the formula —O—, a grouprepresented by the formula —C(O)— or a group represented by the formula—C(O)O— inserted between the carbon atom-carbon atom.
 7. A method forproducing a compound represented by the following formula (p12), whichcomprises reacting a compound represented by the following formula (p5)with a compound represented by the following formula (p4) to obtain acompound represented by the following formula (p3), and then reactingthe compound with a compound represented by the following formula (p2):CH₂(C(O)OZ^(P))₂  (p5)CHR═CR(CH₂)_(n)-G^(P)  (p4)CH(C(O)OZ^(P))₂((CH₂)_(n)CR═CHR)  (p3)CF₂═CFCF₂-J^(P)  (p2)CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12) wherein Z^(P) is a C₁₋₂₀monovalent organic group; R is a hydrogen atom or a C₁₋₂₀ monovalentorganic group, provided that two R's may be the same or different; n is0, 1 or 2; GP is a chlorine atom, a bromine atom or an iodine atom;J^(P) is a chlorine atom, a bromine atom, an iodine atom or a grouprepresented by the formula —OSO₂-L^(P); and L^(P) is a fluorine atom, aC₁₋₁₀ hydrocarbon group or a C₁₋₁₀ fluorinated hydrocarbon group.
 8. Amethod for producing a compound represented by the following formula(12H), which comprises hydrolyzing a compound represented by thefollowing formula (p12):CF₂═CFCF₂C(C(O)OZ^(P))₂(CH₂)_(n)CR═CHR  (p12)CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H) wherein Z^(P) is a C₁₋₂₀monovalent organic group; R is a hydrogen atom or a C₁₋₂₀ monovalentorganic group, provided that two R's may be the same or different; and nis 0, 1 or
 2. 9. A method for producing a compound represented by thefollowing formula (11H), which comprises decarboxylation of a compoundrepresented by the following formula (12H):CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)CF₂═CFCF₂CH(C(O)OH)(CH₂)_(n)CR═CHR  (11H) wherein R is a hydrogen atomor a C₁₋₂₀ monovalent organic group, provided that two R's may be thesame or different; and n is 0, 1 or
 2. 10. A method for producing acompound represented by the following formula (12W), which comprisesreacting a compound represented by the following formula (12H) with acompound represented by the following formula (w):CF₂═CFCF₂C(C(O)OH)₂(CH₂)_(n)CR═CHR  (12H)CH₂═CW^(P) ₂  (w)CF₂═CFCF₂C(C(O)OC(CH₃)W^(P) ₂)₂(CH₂)_(n)CR═CHR  (12W) wherein R is ahydrogen atom or a C₁₋₂₀ monovalent organic group, provided that two R'smay be the same or different; n is 0, 1 or 2; and W^(P) is eachindependently a hydrogen atom or a C₁₋₂₀ monovalent saturatedhydrocarbon group, or two W^(P)'s are groups which form a C₃₋₂₀ bivalentcyclic hydrocarbon group in combination with the carbon atom in theformula.
 11. A method for producing a compound represented by thefollowing formula (11W), which comprises reacting a compound representedby the following formula (11H) with a compound represented by thefollowing formula (w):CF₂═CFCF₂CH(C(O)OH)(CH₂)_(n)CR═CHR  (11H)CH₂═CW^(P) ₂  (w)CF₂═CFCF₂CH(C(O)OC(CH₃)W^(P) ₂)(CH₂)_(n)CR═CHR  (11W) wherein R is ahydrogen atom or a C₁₋₂₀ monovalent organic group, provided that two R'smay be the same or different; n is 0, 1 or 2; and W^(P) is eachindependently a hydrogen atom or a C₁₋₂₀ monovalent saturatedhydrocarbon group, or two W^(P)'s are groups which form a C₃₋₂₀ bivalentcyclic hydrocarbon group in combination with the carbon atom in theformula.